Forty years of Fenske-Hall molecular orbital theory

Theory and Applications of Computational Chemistry

Volumn , Issue , 2005, Pages 1143-1165

  Webster, Charles Edwin ^a   Hall, Michael B ^a  

^a TEXAS A AND M UNIVERSITY   (United States)

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EID: 84885111298     PISSN: None     EISSN: None     Source Type: Book    
DOI: 10.1016/B978-044451719-7/50083-4     Document Type: Chapter

References (52)

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19. The single-point HFR/6-31G, FH, BVP86/6-31G, and B3LYP/6-31G calculations used the B3LYP/6-31G(d) optimized geometry for ferrocene. The FH and B3LYP calculations used experiment geometries for Cp2Ni2(μ-S)2(MnCO)193 (with all-electron 6-31G basis sets for all atoms) and [Ru(CO)4]3[Pd(PR3)]3 (a basis set denoted BS2 with all-electron 6-31G basis sets for C, O, and H; LANL2DZ(d) [24a] for phosphorus; and Couty and Hall modified LANL2DZ [24b] for Ru and Pd) [22]. All HFR and DFT singlepoint calculations used standard double zeta Pople-style basis sets. The DFT calculations were performed with the B3LYP [26] and BVP86 [27] functionals as implemented in Gaussian 03 [28]. Fenske-Hall calculations were performed utilizing a graphical user interface (JIMP) developed to build inputs and view outputs from stand-alone Fenske-Hall (version 5.2) and MOPLOT2 binary executables. Contracted double-zeta basis sets were used for the Mn, Fe, and Ni 4d; Ru and Pd 5d; S and P 3p; and C and O 2p atomic
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28. Adams R.D., Miao S., Smith M.D., Farach H., Webster C.E., Manson J., Hall M.B. Inorg. Chem. 2004, 43:2515.
29. There are actually two nearly degenerate alpha HFR orbitals that contain this Mn character, the HOMO-25 and HOMO-26; they are both a symmetry and mix with two different sets of Ni d combinations. We have rotated these two nearly degenerate orbitals (they differ by only 0.24 kcal mol-1) by 40° to produce two new orbitals, one with mainly Mn(CO)3 character (shown in Fig. 40.6) and the other with mainly Ni character (not shown).
30. Adams R.D., Captain B., Fu W., Hall M.B., Manson J., Smith M.D., Webster C.E. J. Am. Chem. Soc. 2004, 126:5253.
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43. Becke A.D. J. Chem. Phys. 1993, 98:5648. Becke three-parameter exchange functional (B3) and the Lee-Yang-Parr correlation functional (LYP),.
44. Lee C., Yang W., Parr R.G. Phys. Rev. B 1988, 37:785.
45. Hertwig R.H., Koch W. Chem. Phys. Lett. 1997, 268:345. Also, see, concerning the various implementations of B3LYP.
46. Becke exchange functional (B) and the Perdew correlation functional (P86). In Gaussian, when "P86" correlation functional is specified, this keyword combines non-local Perdew correlation with Perdew-Zunger81 local correlation. When "VP86" correlation functional is specified, Gaussian uses VWN5 local correlation instead of Perdew-Zunger81, A.D. Becke, Phys. Rev. A, 38 (1988) 3098; J.P. Perdew, Phys. Rev. B, 33 (1986) 8822, 34 (1986) 7406; J.P. Perdew and A. Zunger, Phys. Rev. B, 23 (1981) 5048.
47. M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, J.A. Montgomery Jr., T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox, H.P. Hratchian, J.B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala, K. Morokuma, G.A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S. Dapprich, A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K.
48. B.E. Bursten, unpublished work, 1980;.
49. The single-point HFR/6-31G, FH, BVP86/6-31G, and B3LYP/6-31G calculations used the B3LYP/6-31G(d) optimized geometry for ferrocene. The FH and B3LYP calculations used experiment geometries for Cp2Ni2(μ-S)2(MnCO)193 (with all-electron 6-31G basis sets for all atoms) and [Ru(CO)4]3[Pd(PR3)]3 (a basis set denoted BS2 with all-electron 6-31G basis sets for C, O, and H; LANL2DZ(d) [24a] for phosphorus; and Couty and Hall modified LANL2DZ [24b] for Ru and Pd) [22]. All HFR and DFT singlepoint calculations used standard double zeta Pople-style basis sets. The DFT calculations were performed with the B3LYP [26] and BVP86 [27] functionals as implemented in Gaussian 03 [28]. Fenske-Hall calculations were performed utilizing a graphical user interface (JIMP) developed to build inputs and view outputs from stand-alone Fenske-Hall (version 5.2) and MOPLOT2 binary executables. Contracted double-zeta basis sets were used for the Mn, Fe, and Ni 4d; Ru and Pd 5d; S and P 3p;
50. There are actually two nearly degenerate alpha HFR orbitals that contain this Mn character, the HOMO-25 and HOMO-26; they are both a symmetry and mix with two different sets of Ni d combinations. We have rotated these two nearly degenerate orbitals (they differ by only 0.24 kcal mol-1) by 40° to produce two new orbitals, one with mainly Mn(CO)3 character (shown in Fig. 40.6) and the other with mainly Ni character (not shown).
51. Becke exchange functional (B) and the Perdew correlation functional (P86). In Gaussian, when "P86" correlation functional is specified, this keyword combines non-local Perdew correlation with Perdew-Zunger81 local correlation. When "VP86" correlation functional is specified, Gaussian uses VWN5 local correlation instead of Perdew-Zunger81, A.D. Becke, Phys. Rev. A, 38 (1988) 3098; J.P. Perdew, Phys. Rev. B, 33 (1986) 8822, 34 (1986) 7406; J.P. Perdew and A. Zunger, Phys. Rev. B, 23 (1981) 5048.
52. M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, J.A. Montgomery Jr., T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox, H.P. Hratchian, J.B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala, K. Morokuma, G.A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S. Dapprich, A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman, J.V. Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J. Cioslowski, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, M. Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, C. Gonzalez and J.A. Pople, Gaussian 03, Revision B.05, Gaussian, Inc., Pittsburgh, PA, 2003.